Process of waterproofing textiles



Patented July 7, 1942 2,289,275 FlCE 2,289,275 PROCESS OF WATERPROOFINGTEXTILES Ludwig Orthner and Gerhard Balle, Frankforton-the-Main, Jo

hann Rosenbach, Wiesbaden,

. and Kurt Bonstedt, Frankfort-on-the-Main, by mesne assignments, to

Germany, .assignors,

General Aniline &

Film

Corporation, New

York, N, Y., a corporati n of Delaware No Drawing.- Application March25, 1939, Serial No. 264,176. In Germany April 2', 1938 4 Claims. (01.3-120) The present invention relates to water-proof textile material andto a process of preparing'it. e have found that natural or artificialfibrous materials of animal or vegetable origin as well as products madetherefrom may be rendered water-repellent by treating them with asolution vor a dispersion of a condensation product of b'etaine-likestructure substituted .at the betain nitrogen by the group andsubjecting the material thus impregated to a heat treatment between 80C. and 150 C.

In the above formula R means a hydrocarbon radical with at least 12carbon atoms which may.

be interrupted by hetero-atoms, for instance An alternative method ofmanufacturing waterrepellent textile materials by means of thecondensation products of betaine-like constitution here in questionconsists in adding oneof the condensation products of betaine-likeconstitution above described to the spinning solution whichis to serveas the making artificial threads.

It is often of special advantage to impregnate the textile material inthe presence of agents of feebly acid action, such as lactic acid,tartaric oxygen or sulfur and X means oxygen or sulfur.

'The compounds which are to be used in the process may be preparedasdescribed in our copending application Serial No. 261,760, Patent No.2,217,846. Compounds suitable for treating the fibrous materials are,for instance, condensation products of betaine-like structure preparedfrom aminocarboxylieacids disubstituted atthe nitrogen atom and forinstance the following halogen methyl compounds: dodecyl chloromethylether, octadecyl chloromethyl ether, dodecyl bromomethyl ether,octylcyclo hexyl chloromethyl ether, the chloromethyl ethers of iiso-octylphenol-monoglycol ether, dodecyldiglycol ether, dodecylhydroxyethyl sulfide, montanalcohol, abietinol and di-hydro'abietinol. are,likewise, suitable sation products from thio-ethers such as, forinstance, dodecyl chloromethylsulfide and octadecyl chloromethylsulfide.

, From the amino-carboxylic acids having tertiary nitrogen, whoseproducts of reaction withthe above mentioned compounds are suitable for'rendering textiles water-repellent, there may be mentioned, forinstance, dimethylamino-acetic acid, dibutylamino-acetic acid,piperidino-acetic acid, morpholino-acetic acid, al'pha-dimethyl-lamino-prop-ionic butyrlc acid.

The textile material is impregnated .with a solution or dispersion ofthe condensation prodacid and gamma-diethylaminoas water-proofing agent,the excess of the solution is removed by squeezing or centrifugingandthe material thus treated is then exposed for some time to atemperature of 80 C. to 150 C.-

The degree of temperature necessary for obtaining a of the waterproofingagent used. Ins'ome cases it may be advantageous first to dry the1mpregnated material at low temperature and then to heat to a highertemperature.

satisfactory efiect depends upon the kind acid, glycolic acid, boricacid or the like. .It is possible thereby to reduce the duration of thesubsequent heat treatment or to obtain a satisfactory eifect even atessentially lower ripening temperature. The textile material may betreated with the acid agents also before or after the im- Dregnationproper.

The condensation products of betaine-like, structure may also be used inadmixturewith other water-proofing agents, for instance, with themethylol-amides of acids of high molecular weight, isocyanates of highmolecular weight or v the addition products of halogen methylethers orhalogen methylamides of high molecular weight with tertiary bases.Furthermore, it is possible to enhance the waterproofing effect of thecondensation products used in the present invention There. thecorresponding condenby adding to the impregnation liquors resin-likecondensation products or the pre-condensation products thereof, forinstance, condensates of urea, thiourea, aniline, melamine,dicyandiamide, phenyliminodiacetic acid-diamide or the like withaldehydes, especially formaldehyde and glyoxal.

In this case not only the water-repellent property of the fibrousmaterial may be enhanced but the not of betaine-like structure which isto be used not diminished even by material acquires a considerablefastness to creasing. The treatment may also be combined with otherprocesses, for instance, by adding to the above described bathssoftening agents, delustering agents, agents known to enhance resistanceto creasing, filling and dressing agents and other agents usuallyapplied in the of textiles.

Various special effects may be obtained which are several washingoperations. 7

The following examples serve to illustrate the 'invention butthey arenot intended to limit it thereto: Y 7

(l) Artificial silk crepe is impregnated at 60 C. with an aqueoussolution of 1 per cent strength of octadecyloxybetaine of the formulaheated for hour at C. to C. Thereby, the material becomes verywater-repellent.

The material lsthen squeezed and parent material 4 for acid methyl esterand wfirst pre-dried at 50 squeezed and heated for 1 hour at 105 (2)Artificial silk fabric is impregnated for 10 minutes at 50 C. with abath containing per litre of water 10 grams of octadecyloxybetaine(which has likewise been applied in Example 1) and 6 cc. of lactic acidof 75 per cent strength. The fabric is then squeezed and subjected for/2 hour to 105 C. to 110 C. After this material becomes very water-proofand water poured thereon immediately runs off in drops. The effectremains undiminished even after several washing operations. I

(3) Artificial silk crepe is impregnated with an alcoholic solutioncontaining per litre 6 'cc. of lactic acid and 10 grams ofoctadecyloxybetaine. The fabric is then freed from the excess of theadherent solvent by centrifuging and heated for 30 minutes at 120 C..

(4) W001 piece goods aretreated with an aqueous solution of theoctadecyloxybetaine of the formula:

(5) Loose viscose artificial silk fibre is im-- short time with anaqueous solution of 1 per cent strength of the product obtained bysaponification of the condensation alpha-dimethyl-amino-propionicdodecyl chloromethyl ether. After centrifuging, the textile material isC. and then heated for 1 product from hourat 130 C.

(6) A mixed fabric wool and artificial silk made from equal parts ofstaple fibre is treated for A minutes with an aqueous solutioncontaining per litre 20 grams of the betaine on, on; 0111115. 5CHI-N10111:. o o o and 8 grams of lactic acid. The material is then C.('7) Artificial silk fabric is impregnated for a short time with anaqueous dispersion of l per cent strength of a mixture consisting ofequal parts of octadecyloxybetaine (cf. Example 1) and stearic acidmethylolamide. The material is then squeezed and heated for /2 hour at135 C.

(8) Fabric from artificial silk staple fibre is impregnated with anaqueous solution containing per litre 100 grams of dimethylol urea, 5

1 grams of tartaric acid and 10 grams of octadecyloxybetaine (of.Example 1). The excess of the impregnating liquor is then removed bycentrifuging and the material exposed to a temperature of 135 C. to 140C. i

(9) A'fabric from viscose staple fiber is impregnated on the foulardwith carbon tetrachloride containing per litre 10 grams of an in--terpolymerization product from maleic acid anhydride and vinyloctadecyiether in the dissolved state. The fabric is then further impregnated,likewise on the foulard, in a second bath containing per litre of water20 grams of octadecyloxybetaine of the formula:

and 5 grams of lactic acid, dried and heated for treatment the 10minutes at 150 C. A fabric is obtained which is very water-repellent,even being resistant to a boiling soap-treatment.

' (10) A fabric prepared from viscose artificial silk and artificialsilk staple fiber made according to the viscose process is treated for ashort time at 50 C. to 60 C. with an aqueous solution containing perlitre 10 grams of octadecyloxybetaine and'6 cc. of lactic acidof '75 percent strength. The material is then squeezed, predried for 1 hour at 60C. and then heated for 20 minutes at 140 C. 4

'(11) Cotton fabric is impregnated with an aqueous solution heated to 60C. containing per litre 6 cc. of lactic acid of '75 per cent strengthand 10 grams of the betaine of the following constitution V he materialis then centrifuged, pre-dried at 50 C. and heated for /z hour at 13 5C. to 140 Cg: CH3 CuHasO-O.CH;.CH.O.CH1.CH.O.CHrliCHaCOO- The materialis squeezed and heated for 1 hour at 140 C.

(13) 11.2 grams of the compound made by saponifying the reaction productfrom octadecylchloromethyl ether and piperidino-acetic acidmethyl esterare added in the form of an aqueous solution of 20 per cent strength to5 kilograms of a viscose solution ready for spinning containing 7.5 percent of cellulose and 6.5 per cent of alkali and the solution is spun inthe usual manner, for instance according to the twobath-process. Thefiber is washed until neutral, dipped into a lactic acid bath of 0.3 percent strength, dried and subjected for 45 minutes at 110 C. to aripening process.

(14) 10 grams of the compound made by saponifying the reaction productfrom octadecylchloromethyl ether and dimethylamino-acetic acid-methylester are added in the form of an aqueous solution of 10 per centstrength to 5 kilograms of a viscose solution ready for spinningcontaining 7.5 per cent of cellulose and 6.5 per cent of alkali and thesolution is spun in the usual manner, for instance according to thetwobath-process. The fiber is washed until neutral, dipped into a lacticacid bath of 0.3 per cent strength, dried and subjected for 45 minutesat 110 C. to a ripening process.

' saponifying "7.5 per cent of cellulose and 6.5 per cent of alkali andthe solution is spun in the usual manner in a Mullen-bath. Thedesulfurized and acidified fiber iswashed until neutral, dipped into asolution of tartaric acid of 0.3 per cent strength and h ated-for 1 hourat C.

nating the textile material 1. The process of manufacturing water repel-I lent textile materialwhich comprises impregnating the textile materialwith a liquor containing a condensation product of betaine-likeconstitution substituted at the betaine nitrogen atom by the group 7 R.X. CH2- wherein R stands for a member of the group consisting ofhydrocarbon radicals and hydrocarbon radicals containing hetero atoms asmembers of their carbon structure the radicals having at least 12 carbonatoms,- X stands for a member of the group consisting of oxygen andsulfur, removingthe excess of the liquor from the textile material andexposing the textile material to a temperature between'about 80 C. andabout 150 C.

2. The process of manufacturing-water'repellent textile material whichcomprises impregwith a liquor containing a weak acid and a condensationproduct of betaine-like constitution substituted at the betaine nitrogenatom by the group R. 2: CH2- wherein R stands for a member of the groupconsisting of hydrocarbon radicals and hydrocarbon radicals containinghetero atoms as mem-' bers of their carbon structure the radicalshaving. at least 12 carbon atoms, X stands for a member of the groupconsisting of oxygen, and sulfur, removing the excess of the liquor fromthe textile material and exposing the textile material to a temperaturebetween about C. v

and about C.

3. A modification of the process described in claim 1 which consists intreating the textile material with a weak acid before impregnating itwith the liquor containing the condensation product of betaine-likeconstitution.

4. A modification of the process described in claim 1 which consists intreating the textile 7 material with a weak acid after impregnating itwith the liquor containing the condensation product of betaine-likeconstitution.

LUDWIG ORTHNER. GERHARD BAILE. JOHANN ROSENBACH. KURT BONSTED'I'.

